EP1373412B1 - Titanium dioxide pigment composition - Google Patents
Titanium dioxide pigment composition Download PDFInfo
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- EP1373412B1 EP1373412B1 EP02727212A EP02727212A EP1373412B1 EP 1373412 B1 EP1373412 B1 EP 1373412B1 EP 02727212 A EP02727212 A EP 02727212A EP 02727212 A EP02727212 A EP 02727212A EP 1373412 B1 EP1373412 B1 EP 1373412B1
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- pigment
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- titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
Definitions
- the invention is directed to a titanium dioxide pigment composition.
- white papers require high opacity (high hiding power), high brightness with as neutral a color as possible and good graying stability (light fastness).
- Titanium dioxide pigments laminate pigments
- the incorporable fraction of these pigments in papers is often limited, since at too high a pigment concentration physical paper properties such. B. sufficient wet tensile strength, no longer meet the requirements. The achievable opacity are therefore limited by the usual pigments.
- Titanium dioxide pigments which are particularly suitable for the production of (matte) emulsion paints, are known ( US Pat. No. 3,510,335 ) that their hiding power can be increased by a special type of post-treatment. They are relatively high (at least 5 wt .-%) coated with silica and alumina, with the type of precipitation as voluminous, porous, flaky, loose, "fluffy” coating is sought. Their graying stability is not sufficient.
- An improved laminate pigment is therefore expected to achieve higher opacity with the same level of pigmentation and unchanged physical properties, in particular wet tear strength. It is of course also a desirable goal if, for a desired opacity, the pigment insert can be reduced with an improved pigment.
- a titanium dioxide pigment composition comprising as pigment type (A) an aftertreated pigment with high graying stability, wherein the graying value CIELAB ⁇ L * (DIN6174) is less than 1.5 after 96 hours exposure in the xenon test, and as pigment type (B) a pigment which has been aftertreated inorganically with Si and Al compounds in fluffy precipitation, where in the case of pigment type (B) the Al content is at least 2% by weight (calculated as Al 2 O 3 ) and the Si content is at least 3% by weight (calculated as SiO 2 ) and the sum of SiO 2 and Al 2 O 3 at least 7 wt .-% (in each case based on the main body) is
- the invention relates to a mixture of a pigment with high graying stability, of a typical laminate pigment (pigment type A), with a particular dispersion paint pigment (pigment type B) characterized by an increased SiO 2 and Al 2 O 3 content in flocculent precipitation.
- Suitable pigment types A are post-treated titanium dioxd pigments whose basic bodies can be prepared by the sulfate (SP) or chloride (CP) process and which preferably have rutile structure.
- the main body does not have to be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0% by weight (calculated as Al 2 O 3 ) and an excess of oxygen in the gas phase the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by doping z.
- the pigments are typically aftertreated with Al, P and / or Si compounds.
- An additional aftertreatment with cerium and / or nitrate and / or zinc compounds serves as well as an annealing at temperatures between 200 and 700 ° C, preferably 400 to 600 ° C, the improvement of the laminate graying stability.
- the pigment type A is characterized by its light fastness value as evaluated in the laminate.
- the graying value CIELAB ⁇ L * (DIN 6174) is less than 1.5 after 96 hours of exposure in the Xenotest or on the Blue Wool Scale (ISO 4586-2), the level is greater than 6.
- Pigments with high graying are commercially available for example under the type designation KRONOS ® 2080 2081, 2084 and 2087th
- Suitable pigment types B are post-treated titanium dioxide pigments whose base bodies can be prepared by the SP or CP process and which preferably have rutile structure.
- the base body is also stabilized: in the CP base body by an Al doping of 0.3 to 3.0 wt .-% (calculated as Al 2 O 3 ) and an excess of oxygen in the gas phase oxidation of TiCl 4 to TiO 2 of 2 to 15 %; in the SP base body by doping z.
- Al, Sb, Nb or Zn In order to obtain a sufficiently high brightness, "light" stabilization with Al is preferred, or with higher Al doping amounts a compensation with antimony).
- the pigment type B is aftertreated relatively high with Al and Si compounds, the Al content (calculated as Al 2 O 3 ) is at least 2 wt .-%, the Si content (calculated as SiO 2 ) at least 3 wt. -%, wherein the sum of the Si and Al fractions (calculated as oxide) is at least 7 wt .-%.
- a particular feature of the pigment type B according to the invention is the flaky, loose formation of the inorganic aftertreatment shell on the base body.
- the most voluminous, porous, flaky, loose, "fluffy” coating eg described in US Pat US Pat. No. 3,510,335
- the opposite of "dense skin treatment” eg described in US Pat US 2,885,366
- the aftertreatment sheath should comprise the TiO 2 particles as completely as possible in order to reduce the undesired photocatalytic effect of the TiO 2 pigment on the surrounding matrix.
- the flocculation of the oxide or oxyhydrate layer in the case of the pigment type B causes an improvement in the pigment distribution in a matrix and contributes significantly to the increase in opacity.
- the loosely precipitated inorganic oxide or oxyhydrate layer on the TiO 2 core acts like a spacer between the scattering particles.
- the pigment type B can also be characterized by property values. Suitable sizes are those which are influenced by the "unevenness" or the closeness of the aftertreatment casing. One measure of unevenness is, for example, the oil count or specific surface area; a measure of the incomplete coverage is, for example, the H 2 SO 4 solubility (the pigment is dispersed in concentrated sulfuric acid and the suspension is kept at 175 ° C. for one hour, after filtration the soluble TiO 2 is determined in the filtrate) of the pigment: the type of pigment B according to the invention has an increased oil absorption value (at least 25) or a relatively high H 2 SO 4 solubility (at least 15% of TiO 2 released).
- a wet breaking load of a paper (produced on the laboratory sheet former) of at least 3.7 N is achieved.
- Pigment based on a non-specifically stabilized by the SP process basic body with rutile structure is a relatively high inorganically aftertreated, by a suitable process procedure (preparation of a ground slurry at pH 10.5, addition of 2.5 wt .-% H 2 SO 4 , and 5.1 wt .-% SiO 2 in the form of sodium silicate solution in 30 minutes, further lowering of the pH after 30 minutes of retention time by 2.5% by weight of H 2 SO 4 , addition of 5.1% by weight of SiO 2 in the form of sodium silicate solution, addition after stirring for 30 minutes of 2.3% by weight of Al 2 O 3 in the form of aluminum sulphate solution in 45 minutes and 90 minutes of stirring, additional addition of 2.9% by weight of Al 2 O 3 in the form of sodium aluminate solution, washing after 60 minutes of retention followed by washing Drying) a flocculent precipitation of the oxide layer is achieved.
- Property values are given in Table 1.
- Pigment based on a not specifically stabilized, ground basic body with rutile structure as in pigment B1.
- Fcculent precipitation by addition of 3.2% by weight of H 2 SO 4 in 30 minutes and then 3.2% by weight of SiO 2 in the form of sodium silicate solution in 30 minutes; then 3.5 wt .-% Al 2 O 3 is added in the form of sodium aluminate solution and then stirred for 30 minutes; Thereafter, 2.0% by weight of Al 2 O 3 in the form of aluminum sulfate solution are added and the suspension is filtered after a retention time of 60 minutes. Further treatment is carried out as for pigment B1; B2 is at the lower limit of pigment type B in terms of "flocculation".
- Pigment based on a with 0.01 wt .-% Al (calculated as Al 2 O 3 ) stabilized SP base. After treatment in 15 minutes with 1.0 wt .-% as P 2 O 5 in the form of disodium hydrogen phosphate solution, in 10 minutes with 1.6 wt .-% Al 2 O 3 in the form of aluminum sulfate solution and in 4 minutes 1.4 wt. -% Al 2 O 3 in the form of sodium aluminate solution.
- Pigment based on a 0.6% by weight Al (calculated as Al 2 O 3 ) stabilized SP base body; it is ground as described under B1, post-treated and dried after addition of 0.4 wt .-% nitrate in the form of sodium nitrate to filter paste and ground; Property values see table 1.
- Pigment based on a with 0.6 wt .-% Al (calculated as Al 2 O 3 ) stabilized SP base. It is made into a paste after grinding and the pH value by 1.9 wt .-% H 2 SO 4 is lowered.
- Pigment based on a with 0.6 wt .-% Al (calculated as Al 2 O 3 ) stabilized SP base. It is pasted after wet grinding and the pH by 2.9 Wt% H 2 SO 4 lowered; in 30 minutes adding 6.0% by weight of SiO 2 in the form of sodium silicate solution; 10 minutes retention time; Addition of 0.7 wt .-% Al 2 O 3 in the form of aluminum sulfate solution in 5 minutes, then 3.7 wt .-% Al 2 O 3 in the form of sodium aluminate solution and then another 1.1 wt .-% Al 2 O. 3 in the form of aluminum sulfate solution, between them is stirred for 10 minutes. Further processing as in B5.
- Table 1 shows typical values. In contrast to a standard laminate pigment (pigment type A), the oil number, H 2 SO 4 solubility, BET surface area are higher.
- the pigments B1 to B7 fulfill the required values for the opacity, expressed here by the values CIELAB L * black and opacity value L, the graying stability in the laminate and in the case of pigment B2 also the wet tear strength in the paper is insufficient.
- a 36.5% aqueous pigment suspension of 146 g of titanium dioxide pigment (or pigment mixture) and 254 g of tap water is prepared. It is based on 30 g of wood pulp (oven-dry) for the testing.
- the appropriate amount Pigment suspension is adapted to the retention and the desired ash content, here 40% ⁇ 1, or the basis weight, here 100 g / m 2 ⁇ 1.
- the procedure and the auxiliaries used are known to the person skilled in the art.
- the sheet to be sealed is immersed in a resin solution and precondensed for 25 seconds in a convection oven at 130 ° C. Similarly, a second impregnation.
- the resin solution is 129-140% of the basis weight.
- the leaf has a residual moisture of 4 to 6 wt .-%.
- the condensed sheets are combined with core papers impregnated with phenolic resin, white and black underlay paper to press packages.
- the laminate structure consisted of 9 layers: paper, paper, core paper, core paper, backing black underlay, core paper, core paper, black / white underlay, paper.
- the packages are pressed by means of a Wickert ® laminate press type 2742 at a temperature of 140 ° C and a pressure of 90 bar for a pressing time of 300 seconds.
- the values are determined with a spectrophotometer (ELREPHO 3300).
- the color values (CIELAB L *, a *, b *) are determined in accordance with DIN 6174 with the aid of ELREPHO ® 3300 colorimeter. It is measured on the side of the laminate on which two papers were pressed together.
- the pigment A1 comparable KRONOS ® 2080 is used purely.
- the production of the laminates is carried out according to the test method described above. In each case papers with 40% ash and 100 g / m 2 basis weight are produced. To adjust the ash content, the necessary amount of TiO 2 suspension is added to the pulp in each experiment. The desired basis weight of 100 g / m 2 is adjusted via the amount of pigment pulp suspension.
- test pigment B1 which corresponds to a standard dispersion paint pigment, is used to 100%.
- the results of experiment 2 are listed in Table 2.
- Pigment B1 shows excellent opacity compared to A1.
- the graying stability is low and unacceptable.
- the leaves also showed very poor wet tensile strength, i. H. they were very soft and tore easily during impregnation.
- the pigment B2 is a less highly surface-treated than the pigment B1 standard dispersion paint pigment.
- the pigment is used neat.
- the results of experiment 3 are listed in Table 2. Laminates with the pigment B2 show a significantly higher opacity compared to pigment A1 as standard, but are less good compared to pigment B1. Pigment B2 also shows insufficient graying stability. There are no disadvantages with respect to wet tear strength.
- a pigment mixture consisting of 70 wt .-% A1 and 30 wt .-% B3 is used.
- the latter is based on a light, slightly stabilized base body with a "classic laminate pigment” and an additional "dispersion paint pigment aftertreatment".
- the results of experiment 5 are in Table 2 listed.
- the abovementioned pigment mixture leads to laminates with markedly improved opacity compared to Experiment 1, the graying stability is at an acceptable level.
- a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B5 is used.
- the latter is a pigment similar to surface treated pigment B4 but made with about 25% less SiO 2 surface treatment.
- the results of experiment 7 are listed in Table 2. This mixture shows due to the lower SiO 2 surface treatment of B5 compared to B4 compared to Experiment 6 inferior opacity with comparable graying stability.
- a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B6 is used.
- Pigment B6 is similarly surface-treated as pigment B2, but with twice the amount of SiO 2 .
- the highly stabilized base body is used as in B4.
- the results of experiment 8 are listed in Table 2.
- the opacity of the laminate pattern with this pigment mixture is significantly higher than that with pure A1.
- the wet tear strength is sufficient, the graying stability is good.
- a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B7 is used.
- the latter pigment is similarly surface-treated as pigment B6.
- the results of experiment 9 are listed in Table 2. Due to an amount of SiO 2 increased compared to Experiment 8, this pigment mixture leads to a laminate with highest opacity values, significantly higher in comparison with pure pigment A1. The graying stability is at a good level. The wet tensile strength of the papers with the above-mentioned pigment mixture is tolerable at the upper limit.
- Titanium dioxide pigment compositions are preferred in which the proportion of the pigment type B is 10 to 90% by weight, particularly preferably 30 to 50% by weight, of the pigment mixture.
- Table 1 ⁇ / b> pigment A1 B1 B2 B3 B4 B5 B6 B7 Al 2 O 3 post-treatment amount (% based on base body 6.5 5.2 5.5 10.2 5.2 5.2 5.5 5.4 SiO 2 post-treatment amount (% based on basic body) ⁇ 0.01 10.2 3.2 3.0 10.2 7.6 6.0 9.0 Oil number (g / 100 g) 18 40 26 29 41 49 35 34 H 2 SO 4 solubility (% -TiO 2 dissolved) 15 19 16 23 19 19 18 19 BET surface area (m 2 / g) 9 49 29 34 45 45 40 53 attempt 1 2 3 4 5 6 7 8th 9 Pigment mixture (in%) A1: 100 - - A1: 70 A1: 70 A1: 70 A1: 70 A1: 70 - B1: 100 B2: 100 B2: 100 B
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Description
Die Erfindung richtet sich auf eine Titandioxid-Pigmentzusammensetzung.The invention is directed to a titanium dioxide pigment composition.
Von weißen Papieren wird für bestimmte Anwendungen eine hohe Opazität (ein hohes Deckvermögen), eine hohe Helligkeit bei möglichst neutralem Farbton und eine gute Vergrauungsstabilität (Lichtechtheit) gefordert. Es sind Titandioxid-Pigmente (Laminatpigmente) mit niedriger Vergrauungstendenz bekannt. Der einarbeitbare Anteil dieser Pigmente in Papiere ist aber häufig begrenzt, da bei einer zu hohen Pigmentkonzentration physikalische Papiereigenschaften, wie z. B. eine ausreichende Nassreißfestigkeit, nicht mehr den Ansprüchen genügen. Der erreichbaren Opazität sind daher mit den üblichen Pigmenten Grenzen gesetzt.For certain applications, white papers require high opacity (high hiding power), high brightness with as neutral a color as possible and good graying stability (light fastness). Titanium dioxide pigments (laminate pigments) with a low tendency to grayness are known. The incorporable fraction of these pigments in papers is often limited, since at too high a pigment concentration physical paper properties such. B. sufficient wet tensile strength, no longer meet the requirements. The achievable opacity are therefore limited by the usual pigments.
Von Titandioxid-Pigmenten, die besonders für die Herstellung von (matten) Dispersionsfarben geeignet sind, ist bekannt (
Es hat sich auch gezeigt, dass weder ein "klassisches Laminatpigment" mit einer zusätzlichen "Dispersionsfarbenpigment"-Nachbehandlung noch ein "Dispersionsfarbenpigment" mit einer zusätzlichen "Laminatpigment"-Nachbehandlung für bestimmte Anwendungen geeignet ist.It has also been found that neither a "classic laminate pigment" with an additional "disperse pigment pigment" post-treatment nor a "disperse pigment" with an additional "laminate pigment" post-treatment is suitable for certain applications.
Von einem verbesserten Laminatpigment wird daher erwartet, dass bei gleicher Pigmentierungshöhe und unveränderten physikalischen Eigenschaften, insbesondere der Nassreißfestigkeit, eine höhere Opazität erzielt wird. Es ist selbstverständlich auch ein erwünschtes Ziel, wenn für eine verlangte Opazität der Pigmenteinsatz mit einem verbesserten Pigment reduziert werden kann.An improved laminate pigment is therefore expected to achieve higher opacity with the same level of pigmentation and unchanged physical properties, in particular wet tear strength. It is of course also a desirable goal if, for a desired opacity, the pigment insert can be reduced with an improved pigment.
Überraschenderweise löst nicht ein Einzelpigment, sondern ein Titandioxid-Pigmentgemisch aus den beiden Pigmenttypen, Laminatpigment und Dispersionsfarbenpigment, die oben genannte Aufgabe. Es wurde gefunden, dass die Zugabe eines speziell hoch nachbehandelten Pigments, einer Art "Boosterpigment", zu einem klassischen Laminatpigment zu einem Pigmentgemisch führt, mit dem die oben beschriebene, gewünschte Verbesserung der Opazität bei ausreichender Vergrauung, Helligkeit und Nassreißfestigkeit erreicht wird.Surprisingly, it is not a single pigment, but a titanium dioxide pigment mixture of the two pigment types, laminate pigment and disperse pigment, which achieves the above-mentioned object. It has been found that the addition of a specially highly-treated pigment, a type of "booster pigment", leads to a classic laminate pigment to give a pigment mixture which achieves the above-described desired improvement in opacity with sufficient graying, brightness and wet tensile strength.
Die Aufgabe wird gelöst durch eine Titandioxid-Pigmentzusammensetzung enthaltend als Pigmenttyp (A) ein nachbehandeltes Pigment mit hoher Vergrauunsgsstabilität, wobei der Vergrauungswert CIELAB ΔL* (DIN6174) kleiner ist als 1,5 nach 96 Stunden Belichtung im Xenontest, und als Pigmenttyp (B) ein mit Si- und Al-Verbindungen in flockiger Auffällung anorganisch nachbehandeltes Pigment, wobei bei Pigmenttyp (B) der Al-Gehalt mindestens 2 Gew.-% (gerechnet als Al2O3) und der Si-Gehalt mindestens 3 Gew.-% (gerechnet als SiO2) und die Summe aus SiO2 und Al2O3 mindestens 7 Gew.-% (jeweils bezogen auf den Grundkörper) beträgtThe object is achieved by a titanium dioxide pigment composition comprising as pigment type (A) an aftertreated pigment with high graying stability, wherein the graying value CIELAB ΔL * (DIN6174) is less than 1.5 after 96 hours exposure in the xenon test, and as pigment type (B) a pigment which has been aftertreated inorganically with Si and Al compounds in fluffy precipitation, where in the case of pigment type (B) the Al content is at least 2% by weight (calculated as Al 2 O 3 ) and the Si content is at least 3% by weight (calculated as SiO 2 ) and the sum of SiO 2 and Al 2 O 3 at least 7 wt .-% (in each case based on the main body) is
Die Erfindung betrifft eine Mischung eines Pigments mit hoher Vergrauungsstabilität, eines typischen Laminatpigments (Pigmenttyp A), mit einem besonderen Dispersionsfarbenpigment (Pigmenttyp B), das durch einen erhöhten SiO2- und Al2O3-Gehalt in flockiger Auffällung gekennzeichnet ist.The invention relates to a mixture of a pigment with high graying stability, of a typical laminate pigment (pigment type A), with a particular dispersion paint pigment (pigment type B) characterized by an increased SiO 2 and Al 2 O 3 content in flocculent precipitation.
Es werden damit verbesserte Werte hinsichtlich Opazität bei ausreichender Vergrauung, Helligkeit und Nassreißfestigkeit erreicht. Aus der Anhebung der Opazität bei gleicher TiO2-Einsatzmenge bzw. der Möglichkeit, eine unveränderte Opazität mit reduziertem TiO2-Pigmenteinsatz zu erzielen, ergeben sich sowohl technische als auch wirtschaftliche Vorteile.Thus, improved opacity values with sufficient graying, brightness and wet tensile strength are achieved. Increasing the opacity with the same amount of TiO 2 used or the possibility of achieving an unchanged opacity with a reduced use of TiO 2 pigment results in both technical and economic advantages.
Weitere vorteilhafte Ausgestaltungen sind in den Unteransprüchen beschrieben. Die Erfindung ist im Folgenden weiter beispielhaft erläutert.Further advantageous embodiments are described in the subclaims. The invention is further exemplified below.
Als Pigmenttyp A kommen nachbehandelte Titandioxd-Pigmente in Frage, deren Grundkörper nach dem Sulfat(SP)- oder Chlorid(CP)-Verfahren hergestellt sein können und die bevorzugt Rutilstruktur haben. Der Grundkörper muss nicht stabilisiert sein, jedoch ist eine spezielle Stabilisierung bevorzugt: beim CP-Grundkörper durch eine Al-Dotierung von 0,3 - 3,0 Gew.-% (gerechnet als Al2O3) und einen Sauerstoffüberschuss in der Gasphase bei der Oxidation des Titantetrachlorids zu Titandioxid von mindestens 2 %; beim SP-Grundkörper durch eine Dotierung z. B. mit Al, Sb, Nb oder Zn (um eine hinreichend hohe Helligkeit zu erhalten, ist eine "leichte" Stabilisierung mit Al bevorzugt bzw. bei höheren Al-Dotierungsmengen eine Kompensation mit Antimon).Suitable pigment types A are post-treated titanium dioxd pigments whose basic bodies can be prepared by the sulfate (SP) or chloride (CP) process and which preferably have rutile structure. The main body does not have to be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0% by weight (calculated as Al 2 O 3 ) and an excess of oxygen in the gas phase the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by doping z. B. with Al, Sb, Nb or Zn (to obtain a sufficiently high brightness, a "light" stabilization with Al is preferred or at higher Al doping amounts compensation with antimony).
Die Pigmente sind typischerweise mit Al-, P- und/oder Si-Verbindungen anorganisch nachbehandelt. Eine zusätzliche Nachbehandlung mit Cer- und/oder Nitrat- und/oder Zinkverbindungen dient ebenso wie eine Temperung bei Temperaturen zwischen 200 und 700 °C, bevorzugt 400 bis 600 °C, der Verbesserung der Laminatvergrauungsstabilität.The pigments are typically aftertreated with Al, P and / or Si compounds. An additional aftertreatment with cerium and / or nitrate and / or zinc compounds serves as well as an annealing at temperatures between 200 and 700 ° C, preferably 400 to 600 ° C, the improvement of the laminate graying stability.
Der Pigmenttyp A wird durch seinen Lichtechtheitswert, beurteilt im Laminat, charakterisiert. Der Vergrauungswert CIELAB ΔL* (DIN 6174) ist kleiner 1,5 nach 96 Stunden Belichtung im Xenotest bzw. auf der Blauen Wollskala (ISO 4586-2) ist die Stufe größer 6.The pigment type A is characterized by its light fastness value as evaluated in the laminate. The graying value CIELAB ΔL * (DIN 6174) is less than 1.5 after 96 hours of exposure in the Xenotest or on the Blue Wool Scale (ISO 4586-2), the level is greater than 6.
Pigmente mit hoher Vergrauungsstabilität (Pigmenttyp A) sind im Handel beispielsweise unter der Typenbezeichnung KRONOS® 2080, 2081, 2084 und 2087 erhältlich.Pigments with high graying (pigment type A) are commercially available for example under the type designation KRONOS ® 2080 2081, 2084 and 2087th
Als Pigmenttyp B kommen nachbehandelte Titandioxid-Pigmente in Frage, deren Grundkörper nach dem SP- oder CP-Verfahren hergestellt sein können und die bevorzugt Rutilstruktur haben. Bevorzugt ist der Grundkörper auch stabilisiert: beim CP-Grundkörper durch eine Al-Dotierung von 0,3 - 3,0 Gew.-% (gerechnet als Al2O3) und einen Sauerstoffüberschuss bei der Gasphasenoxidation des TiCl4 zu TiO2 von 2 bis 15 %; beim SP-Grundkörper durch eine Dotierung z. B. mit Al, Sb, Nb oder Zn (um eine hinreichend hohe Helligkeit zu erhalten, ist eine "leichte" Stabilisierung mit Al bevorzugt bzw. bei höheren Al-Dotierungsmengen eine Kompensation mit Antimon).Suitable pigment types B are post-treated titanium dioxide pigments whose base bodies can be prepared by the SP or CP process and which preferably have rutile structure. Preferably, the base body is also stabilized: in the CP base body by an Al doping of 0.3 to 3.0 wt .-% (calculated as Al 2 O 3 ) and an excess of oxygen in the gas phase oxidation of TiCl 4 to TiO 2 of 2 to 15 %; in the SP base body by doping z. With Al, Sb, Nb or Zn (In order to obtain a sufficiently high brightness, "light" stabilization with Al is preferred, or with higher Al doping amounts a compensation with antimony).
Der Pigmenttyp B ist relativ hoch mit Al- und Si-Verbindungen anorganisch nachbehandelt, der Al-Gehalt (gerechnet als Al2O3) beträgt mindestens 2 Gew.-%, der Si-Gehalt (gerechnet als SiO2) mindestens 3 Gew.-%, wobei die Summe der Si- und Al-Anteile (gerechnet als Oxid) mindestens 7 Gew.-% beträgt.The pigment type B is aftertreated relatively high with Al and Si compounds, the Al content (calculated as Al 2 O 3 ) is at least 2 wt .-%, the Si content (calculated as SiO 2 ) at least 3 wt. -%, wherein the sum of the Si and Al fractions (calculated as oxide) is at least 7 wt .-%.
Ein besonderes Kennzeichen des Pigmenttyps B ist erfindungsgemäß die flockige, lockere Ausbildung der anorganischen Nachbehandlungshülle auf dem Grundkörper. Es wird eine möglichst voluminöse, poröse, flockige, lockere, "fluffy" Beschichtung (z. B. beschrieben in
Der Pigmenttyp B kann auch durch Eigenschaftswerte charakterisiert werden. Dazu eignen sich Größen, die von der "Unebenheit" bzw. der Geschlossenheit der Nachbehandlungshülle beeinflusst werden. Ein Maß der Unebenheit ist beispielsweise die Ölzahl oder die spezifische Oberfläche; ein Maß für die unvollständige Abdeckung ist beispielsweise die H2SO4-Löslichkeit (das Pigment wird in konzentrierter Schwefelsäure dispergiert und die Suspension eine Stunde bei 175 °C gehalten; nach Filtration wird im Filtrat das lösliche TiO2 bestimmt) des Pigments: Der Pigmenttyp B gemäß der Erfindung hat eine erhöhte Ölzahl (mindestens 25) oder eine relativ hohe H2SO4-Löslichkeit (mindestens 15 % TiO2 gelöst).The pigment type B can also be characterized by property values. Suitable sizes are those which are influenced by the "unevenness" or the closeness of the aftertreatment casing. One measure of unevenness is, for example, the oil count or specific surface area; a measure of the incomplete coverage is, for example, the H 2 SO 4 solubility (the pigment is dispersed in concentrated sulfuric acid and the suspension is kept at 175 ° C. for one hour, after filtration the soluble TiO 2 is determined in the filtrate) of the pigment: the type of pigment B according to the invention has an increased oil absorption value (at least 25) or a relatively high H 2 SO 4 solubility (at least 15% of TiO 2 released).
Die Pigmentmischung gemäß der Erfindung kann auch durch Eigenschaftswerte, beurteilt im Laminat, charakterisiert werden:The pigment mixture according to the invention can also be characterized by property values assessed in the laminate:
Die folgenden Werte beziehen sich auf Papiere mit einem Aschegehalt von 40 ± 1% und einem Flächengewicht von 100 ± 1 g/m2
- a) Opazität
- i) CIELAB L* schwarz ≥ 90,0
- ii) Opazitätswert L ≥ 90,7
- b) Lichtstabilität
- i) Blaue Wollskala: Stufe > 6
- ii) CIELAB ΔL* < 2,0
- a) opacity
- i) CIELAB L * black ≥ 90.0
- ii) Opacity value L ≥ 90.7
- b) light stability
- i) Blue wool scale: Level> 6
- ii) CIELAB ΔL * <2.0
Mit einem erfindungsgemäßen Pigmentgemisch wird eine Nassbruchlast eines Papiers (hergestellt am Laborblattbildner) von mindestens 3,7 N erreicht.With a pigment mixture according to the invention, a wet breaking load of a paper (produced on the laboratory sheet former) of at least 3.7 N is achieved.
Alle Anforderungen aus dem Laminatbereich werden durch das erfindungsgemäße Pigmentgemisch erfüllt.All requirements from the laminate area are met by the pigment mixture according to the invention.
Weitere vorteilhafte Verbesserungen für den Pigmenttyp B, besonders hinsichtlich der Laminatvergrauungsstabilität, sind insbesondere durch die nachfolgenden Maßnahmen möglich:
- a) Zusätzliche Zugaben von Cer, Zink- oder Nitratverbindungen während der Nachbehandlung, oder im Falle von Nitrat besonders bevorzugt zur Filterpaste vor der Trocknung. Ebenso ist die Zugabe von Nitratverbindungen während der abschließenden Mahlung des Pigments möglich.
- b) Vor der Nachbehandlung, die im Sinne dieser Erfindung zu der lockeren "fluffy" Nachbehandlungshülle aus SiO2 und Al2O3 führt, eine erste Nachbehandlung, die derjenigen vom Pigmenttyp A entspricht.
- a) Additional additions of cerium, zinc or nitrate compounds during the aftertreatment, or in the case of nitrate particularly preferred to the filter paste before drying. Likewise, the addition of nitrate compounds during the final grinding of the pigment is possible.
- b) Before the aftertreatment, which leads to the loose "fluffy" aftertreatment casing of SiO 2 and Al 2 O 3 for the purposes of this invention, a first after-treatment which corresponds to that of the pigment type A.
Nach dem CP-Verfahren hergestelltes, mit 5,5 - 7,5 Gew.-% * einer Aluminiumverbindung (gerechnet als Al2O3), 1,0 - 3,0 Gew.-% einer Phosphorverbindung (gerechnet als P2O5) und zusätzlich mit 0,18 - 0,24 Gew.-% eines Nitrat nachbehandeltes Rutilpigment; die Eigenschaftswerte sind in Tabelle 1 zusammengefasst. Ein ähnliches typisches "Laminatpigment" ist beispielsweise unter der Bezeichnung KRONOS® 2080 im Handel.
* alle Gewichtsprozentangaben für Nachbehandlungssubstanzen beziehen sich in den Beispielen auf den eingesetzten GrundkörperMade by the CP method, with 5.5 - 7.5 wt .-% * of an aluminum compound (calculated as Al 2 O 3 ), 1.0-3.0% by weight of a phosphorus compound (calculated as P 2 O 5 ) and additionally with 0.18-0.24% by weight of a rutile aftertreated rutile pigment; the property values are summarized in Table 1. A similar typical "laminating paper pigment" is, for example, under the name Kronos ® 2080 commercially.
* All weight percentages for aftertreatment substances in the examples refer to the basic body used
Pigment auf der Basis eines nicht speziell stabilisierten nach dem SP-Verfahren hergestellten Grundkörpers mit Rutilstruktur. Das Pigment ist verhältnismäßig hoch anorganisch nachbehandelt, wobei durch eine geeignete Verfahrensführung (Herstellung einer gemahlenen Slurry bei pH-Wert 10,5; Zugabe von 2,5 Gew.-% H2SO4; und 5,1 Gew.-% SiO2 in Form von Natriumsilikatlösung in 30 Minuten; weitere pH-Absenkung nach 30 Minuten Retentionszeit durch 2,5 Gew.-% H2SO4; Zugabe von 5,1 Gew.-% SiO2 in Form von Natriumsilikatlösung; nach 30 Minuten Rühren Zugabe von 2,3 Gew.-% Al2O3 in Form von Aluminiumsulfatlösung in 45 Minuten und 90 Minuten Rühren; nochmalige Zugabe von 2,9 Gew.-% Al2O3 in Form von Natriumaluminatlösung; nach 60 Minuten Retentionszeit folgt Waschung und Trocknung) eine flockige Auffällung der Oxidschicht erreicht wird. Eigenschaftswerte sind in der Tabelle 1 angegeben.Pigment based on a non-specifically stabilized by the SP process basic body with rutile structure. The pigment is a relatively high inorganically aftertreated, by a suitable process procedure (preparation of a ground slurry at pH 10.5, addition of 2.5 wt .-% H 2 SO 4 , and 5.1 wt .-% SiO 2 in the form of sodium silicate solution in 30 minutes, further lowering of the pH after 30 minutes of retention time by 2.5% by weight of H 2 SO 4 , addition of 5.1% by weight of SiO 2 in the form of sodium silicate solution, addition after stirring for 30 minutes of 2.3% by weight of Al 2 O 3 in the form of aluminum sulphate solution in 45 minutes and 90 minutes of stirring, additional addition of 2.9% by weight of Al 2 O 3 in the form of sodium aluminate solution, washing after 60 minutes of retention followed by washing Drying) a flocculent precipitation of the oxide layer is achieved. Property values are given in Table 1.
Pigment auf der Basis eines nicht speziell stabilisierten, gemahlenen Grundkörpers mit Rutilstruktur wie in Pigment B1. Flockige Auffällung durch Zugabe von 3,2 Gew.-% H2SO4 in 30 Minuten und danach 3,2 Gew.-% SiO2 in Form von Natriumsilikatlösung in 30 Minuten; anschließend wird 3,5 Gew.-% Al2O3 in Form von Natriumaluminat-Lösung zugegeben und danach 30 Minuten gerührt; danach werden 2,0 Gew.-% Al2O3 in Form von Aluminiumsulfat-Lösung zugegeben und die Suspension nach einer Retentionszeit von 60 Minuten filtriert. Die weitere Behandlung erfolgt wie bei Pigment B1; B2 liegt hinsichtlich "Flockigkeit" an der unteren Grenze des Pigmenttyps B.Pigment based on a not specifically stabilized, ground basic body with rutile structure as in pigment B1. Fcculent precipitation by addition of 3.2% by weight of H 2 SO 4 in 30 minutes and then 3.2% by weight of SiO 2 in the form of sodium silicate solution in 30 minutes; then 3.5 wt .-% Al 2 O 3 is added in the form of sodium aluminate solution and then stirred for 30 minutes; Thereafter, 2.0% by weight of Al 2 O 3 in the form of aluminum sulfate solution are added and the suspension is filtered after a retention time of 60 minutes. Further treatment is carried out as for pigment B1; B2 is at the lower limit of pigment type B in terms of "flocculation".
Pigment auf der Basis eines mit 0,01 Gew.-% Al (gerechnet als Al2O3) stabilisierten SP-Grundkörpers. Nachbehandlung in 15 Minuten mit 1,0 Gew.-% als P2O5 in Form von Dinatriumhydrogenphosphatlösung, in 10 Minuten mit 1,6 Gew.-% Al2O3 in Form von Aluminiumsulfatlösung und in 4 Minuten 1,4 Gew.-% Al2O3 in Form von Natriumaluminatlösung. Nach der Einstellung des pH-Wertes auf 4 mit H2SO4 in 30 Minuten, Zugabe von 3,0 Gew.-% SiO2 in Form von Natriumsilikatlösung zusammen mit Aluminiumsulfatlösung (100 g Al2O3) in einer Menge, dass der pH von 4 konstant bleibt, sowie folgend Zugabe in 12 Minuten 4,7 Gew.-% Al2O3 in Form von Natriumaluminatlösung und danach nochmals in 15 Minuten von 2,2 Gew.-% Al2O3 in Form von Aluminiumsulfatlösung. Eigenschaftswerte siehe Tabelle 1.Pigment based on a with 0.01 wt .-% Al (calculated as Al 2 O 3 ) stabilized SP base. After treatment in 15 minutes with 1.0 wt .-% as P 2 O 5 in the form of disodium hydrogen phosphate solution, in 10 minutes with 1.6 wt .-% Al 2 O 3 in the form of aluminum sulfate solution and in 4 minutes 1.4 wt. -% Al 2 O 3 in the form of sodium aluminate solution. After adjusting the pH to 4 with H 2 SO 4 in 30 minutes, add 3.0% by weight of SiO 2 in the form of sodium silicate solution together with aluminum sulfate solution (100 g of Al 2 O 3 ) in an amount such that the pH of 4 remains constant, followed by addition in 12 minutes 4.7 wt .-% Al 2 O 3 in the form of sodium aluminate solution and then again in 15 minutes of 2.2 wt .-% Al 2 O 3 in the form of aluminum sulfate solution. Property values see table 1.
Pigment auf der Basis eines mit 0,6 Gew.-% Al (gerechnet als Al2O3) stabilisierten SP-Grundkörpers; es wird wie unter B1 beschrieben, gemahlen, nachbehandelt und nach Zugabe von 0,4 Gew.-% Nitrat in Form von Natriumnitrat zur Filterpaste getrocknet und gemahlen; Eigenschaftswerte siehe Tabelle 1.Pigment based on a 0.6% by weight Al (calculated as Al 2 O 3 ) stabilized SP base body; it is ground as described under B1, post-treated and dried after addition of 0.4 wt .-% nitrate in the form of sodium nitrate to filter paste and ground; Property values see table 1.
Pigment auf der Basis eines mit 0,6 Gew.-% Al (gerechnet als Al2O3) stabilisierten SP-Grundkörpers. Es wird nach Mahlung angeteigt und der pH-Wert durch 1,9 Gew.-% H2SO4 abgesenkt. Zugabe in 20 Minuten von 3,8 Gew.-% SiO2 in Form von Natriumsilikatlösung, nach 10 Minuten Retentionszeit Zugabe von 1,9 Gew.-% H2SO4 zur Absenkung des pH-Wertes; erneute Zugabe von 3,8 Gew.-% SiO2 in Form von Natriumsilikat; nach 10 Minuten Rührdauer Zugabe von 2,0 Gew.-% Al2O3 in Form von Aluminiumsulfatlösung in 10 Minuten, danach Zugabe von 3,2 Gew.-% Al2O3 in der Form von Natriumaluminat; nach 60 Minuten Retentionszeit Filtration, Waschung, Trocknung, Mahlung.Pigment based on a with 0.6 wt .-% Al (calculated as Al 2 O 3 ) stabilized SP base. It is made into a paste after grinding and the pH value by 1.9 wt .-% H 2 SO 4 is lowered. Addition in 20 minutes of 3.8 wt .-% SiO 2 in the form of sodium silicate solution, after 10 minutes retention time addition of 1.9 wt .-% H 2 SO 4 to lower the pH; re-addition of 3.8% by weight of SiO 2 in the form of sodium silicate; after stirring for 10 minutes, add 2.0% by weight of Al 2 O 3 in the form of aluminum sulfate solution in 10 minutes, then add 3.2% by weight of Al 2 O 3 in the form of sodium aluminate; after 60 minutes retention time filtration, washing, drying, grinding.
Pigment auf der Basis eines mit 0,6 Gew.-% Al (gerechnet als Al2O3) stabilisierten SP-Grundkörpers. Es wird nach Nassmahlung angeteigt und der pH-Wert durch 2,9 Gew.-% H2SO4 abgesenkt; in 30 Minuten Zugabe von 6,0 Gew.-% SiO2 in Form von Natriumsilikatlösung; 10 Minuten Retentionszeit; Zugabe von 0,7 Gew.-% Al2O3 in Form von Aluminiumsulfatlösung in 5 Minuten, danach 3,7 Gew.-% Al2O3 in Form von Natriumaluminatlösung und anschließend weitere 1,1 Gew.-% Al2O3 in Form von Aluminiumsulfatlösung, dazwischen wird jeweils 10 Minuten gerüht. Die weitere Verarbeitung wie in B5.Pigment based on a with 0.6 wt .-% Al (calculated as Al 2 O 3 ) stabilized SP base. It is pasted after wet grinding and the pH by 2.9 Wt% H 2 SO 4 lowered; in 30 minutes adding 6.0% by weight of SiO 2 in the form of sodium silicate solution; 10 minutes retention time; Addition of 0.7 wt .-% Al 2 O 3 in the form of aluminum sulfate solution in 5 minutes, then 3.7 wt .-% Al 2 O 3 in the form of sodium aluminate solution and then another 1.1 wt .-% Al 2 O. 3 in the form of aluminum sulfate solution, between them is stirred for 10 minutes. Further processing as in B5.
Dieses Pigment unterscheidet sich von Pigment B6 nur in der Höhe der Nachbehandlungssubstanzen. Die Mengen sind:
- 4,7 % H2SO4
- 9,0 % SiO2 als Natriumsilikat in 45 Minuten
- 0,7 % Al2O3 als Aluminiumsulfat
- 3,8 % Al2O3 als Natriumaluminat
- 0,9 % Al2O3 als Aluminiumsulfat
- 4.7% H 2 SO 4
- 9.0% SiO 2 as sodium silicate in 45 minutes
- 0.7% Al 2 O 3 as aluminum sulfate
- 3.8% Al 2 O 3 as sodium aluminate
- 0.9% Al 2 O 3 as aluminum sulfate
In der Tabelle 1 sind typische Werte zusammengestellt. Im Gegensatz zu einem Standard-Laminatpigment (Pigmenttyp A) sind Ölzahl, H2SO4-Löslichkeit, BET-Oberfläche höher.Table 1 shows typical values. In contrast to a standard laminate pigment (pigment type A), the oil number, H 2 SO 4 solubility, BET surface area are higher.
Die Pigmente B1 bis B7 erfüllen zwar die geforderten Werte für die Opazität, hier ausgedrückt durch die Werte CIELAB L* schwarz und Opazitätswert L, jedoch ist die Vergrauungsstabilität im Laminat sowie bei Pigment B2 auch die Nassreißfestigkeit im Papier unzureichend.Although the pigments B1 to B7 fulfill the required values for the opacity, expressed here by the values CIELAB L * black and opacity value L, the graying stability in the laminate and in the case of pigment B2 also the wet tear strength in the paper is insufficient.
Es wird eine 36,5 %ige, wässrige Pigmentsuspension aus 146 g Titandioxid-Pigment (bzw. Pigmentgemisch) und 254 g Leitungswasser hergestellt. Es werden 30 g Zellstoff (ofentrocken) für die Testung zugrunde gelegt. Die entsprechende Menge Pigmentsuspension wird an die Retention und den gewünschten Aschegehalt, hier 40 % ± 1, bzw. das Flächengewicht, hier 100 g/m2 ± 1, angepasst. Die Vorgehensweise und die eingesetzten Hilfsstoffe sind dem Fachmann bekannt. Das zu beharzende Blatt wird in eine Harzlösung eingetaucht und für 25 Sekunden im Umlufttrockenschrank bei 130 °C vorkondensiert. Ähnlich erfolgt eine zweite Imprägnierung. Die Harzlösung beträgt 129 - 140 % des Flächengewichts. Das Blatt hat eine Restfeuchte von 4 - 6 Gew.-%. Die kondensierten Blätter werden mit Phenolharz getränkten Kernpapieren, weißem und schwarzem Underlay Papier zu Presspaketen zusammengelegt.
Bei dem Versuch bestand der Laminataufbau aus 9 Schichten: Papier, Papier, Kernpapier, Kernpapier, Gegenzug aus schwarzem Underlay, Kernpapier, Kernpapier, schwarz/weißes Underlay, Papier.
Das Pressen der Pakete erfolgt mit Hilfe einer Wickert® Laminat-Presse Typ 2742 bei einer Temperatur von 140 °C und einem Druck von 90 bar für eine Presszeit von 300 Sekunden.A 36.5% aqueous pigment suspension of 146 g of titanium dioxide pigment (or pigment mixture) and 254 g of tap water is prepared. It is based on 30 g of wood pulp (oven-dry) for the testing. The appropriate amount Pigment suspension is adapted to the retention and the desired ash content, here 40% ± 1, or the basis weight, here 100 g / m 2 ± 1. The procedure and the auxiliaries used are known to the person skilled in the art. The sheet to be sealed is immersed in a resin solution and precondensed for 25 seconds in a convection oven at 130 ° C. Similarly, a second impregnation. The resin solution is 129-140% of the basis weight. The leaf has a residual moisture of 4 to 6 wt .-%. The condensed sheets are combined with core papers impregnated with phenolic resin, white and black underlay paper to press packages.
In the experiment, the laminate structure consisted of 9 layers: paper, paper, core paper, core paper, backing black underlay, core paper, core paper, black / white underlay, paper.
The packages are pressed by means of a Wickert ® laminate press type 2742 at a temperature of 140 ° C and a pressure of 90 bar for a pressing time of 300 seconds.
Die Opazität ist ein Maß für die Lichtdurchlässigkeit oder Transmission des Papiers. Als Maß der Opazität der Laminate werden gewählt:
- i) CIELAB L* schwarz, die Helligkeit der Laminate gemessen über schwarzem Underlay-Papier.
- ii) Opazitätswert L [%] = Y schwarz / Y weiß .100 ermittelt aus dem Y-Wert gemessen über schwarzem Underlay-Papier (Y schwarz) und dem Y-Wert gemessen über weißem Underlay-Papier (Yweiß).
- i) CIELAB L * black, the brightness of the laminates measured over black underlay paper.
- ii) Opacity value L [%] = Y black / Y white .100 determined from the Y value measured over black underlay paper (Y black) and the Y value measured over white underlay paper (Y white ).
Die Werte werden mit einem Spektralphotometer (ELREPHO 3300) ermittelt.The values are determined with a spectrophotometer (ELREPHO 3300).
Zur Beurteilung der Vergrauungsstabilität (Lichtechtheit) der Titandioxid-Pigmente bzw. Pigmentmischungen werden die entsprechenden Laminatmuster in einem XENOTEST 150S belichtet. Für die Beurteilung wird die Seite des Laminats, auf der zwei Papiere miteinander verpresst werden, gemessen.
- i) Vergrauung CIELAB ΔL*
Es werden die Helligkeit CIELAB L* nach DIN 6174 vor und nach einer Dauer von 96 Stunden Belichtung im Xenotest gemessen. Die Lichtquelle ist eine Xenon-Bogen-Lampe. Die Temperatur im Innenraum des Gerätes liegt bei 23 ± 3 °C, die relative Feuchte bei 65 ± 5 %. Die Proben werden im "Wendelauf" belichtet. - ii) Blaue Wollskala
Es wird in Anlehnung an ISO 4586-2 (1995) mit Hilfe der "Blauen Wollskala" die Lichtechtheit beurteilt.
- i) graying CIELAB ΔL *
The brightness CIELAB L * according to DIN 6174 is measured before and after a duration of 96 hours exposure in Xenotest. The light source is a xenon arc lamp. The temperature inside the device is 23 ± 3 ° C, the relative humidity at 65 ± 5%. The samples are exposed in the "spiral run". - ii) Blue wool scale
Based on ISO 4586-2 (1995), the lightfastness is assessed using the "blue wool scale".
Zur Beurteilung der Nassreißfestigkeit der Papiere werden diese zunächst 24 Stunden bei 105 °C gelagert ("gereift"). Prüfstreifen von 15 mm Breite werden 5 Minuten in destilliertem Wasser gewässert. Anschließend werden die nassen Streifen mit Hilfe einer Zugprüfmaschine auf ihre Nassbruchlast geprüft. Die Nassreißfestigkeit wird in Newton angegeben.To assess the wet tensile strength of the papers they are first stored for 24 hours at 105 ° C ("matured"). Test strips of 15 mm width are watered in distilled water for 5 minutes. Subsequently, the wet strips are tested for their wet breaking load with the aid of a tensile testing machine. The wet tensile strength is given in Newtons.
Die Farbwerte (CIELAB L*, -a*, -b*) werden nach DIN 6174 mit Hilfe des ELREPHO® 3300-Farbmeßgerätes bestimmt. Es wird auf der Seite des Laminats, auf der zwei Papiere miteinander verpresst wurden, gemessen.The color values (CIELAB L *, a *, b *) are determined in accordance with DIN 6174 with the aid of ELREPHO ® 3300 colorimeter. It is measured on the side of the laminate on which two papers were pressed together.
Das Pigment A1, vergleichbar KRONOS® 2080, wird pur eingesetzt. Die Herstellung der Laminate erfolgt gemäß der zuvor beschriebenen Testmethode. Es werden jeweils Papiere mit 40 % Asche und 100 g/m2 Flächengewicht hergestellt. Um den Aschegehalt einzustellen, wird beim jeweiligen Versuch die notwendige Menge TiO2-Suspension zur Pulpe zugesetzt. Das angestrebte Flächengewicht von 100 g/m2 wird über die Menge Pigment-Zellstoffsuspension eingestellt.The pigment A1, comparable KRONOS ® 2080 is used purely. The production of the laminates is carried out according to the test method described above. In each case papers with 40% ash and 100 g / m 2 basis weight are produced. To adjust the ash content, the necessary amount of TiO 2 suspension is added to the pulp in each experiment. The desired basis weight of 100 g / m 2 is adjusted via the amount of pigment pulp suspension.
Die jeweils eingesetzten Mengen TiO2-Suspension sowie die Menge Pigment-Zellstoff-Suspension sind in Tabelle 2 aufgeführt.The amounts of TiO 2 suspension used in each case and the amount of pigment-pulp suspension are listed in Table 2.
Das Versuchspigment B1, das einem Standard-Dispersionsfarbenpigment entspricht, wird zu 100 % eingesetzt. Die Ergebnisse von Versuch 2 sind in Tabelle 2 aufgeführt. Das Pigment B1 zeigt eine hervorragende Opazität im Vergleich zu A1. Die Vergrauungsstabilität ist aber niedrig und nicht akzeptabel. Die Blätter zeigten außerdem eine sehr schlechte Nassreißfestigkeit, d. h. sie waren sehr weich und zerrissen leicht während der Imprägnierung.The test pigment B1, which corresponds to a standard dispersion paint pigment, is used to 100%. The results of experiment 2 are listed in Table 2. Pigment B1 shows excellent opacity compared to A1. The graying stability is low and unacceptable. The leaves also showed very poor wet tensile strength, i. H. they were very soft and tore easily during impregnation.
Das Pigment B2 ist ein im Vergleich zum Pigment B1 weniger hoch oberflächenbehandeltes Standard-Dispersionsfarbenpigment. Das Pigment wird pur eingesetzt. Die Ergebnisse von Versuch 3 sind in Tabelle 2 aufgeführt. Laminate mit dem Pigment B2 zeigen eine deutlich höhere Opazität verglichen mit Pigment A1 als Standard, sind aber weniger gut im Vergleich zu Pigment B1. Auch Pigment B2 zeigt eine nicht ausreichende Vergrauungsstabilität. Es gibt keine Nachteile bezüglich der Nassreißfestigkeit.The pigment B2 is a less highly surface-treated than the pigment B1 standard dispersion paint pigment. The pigment is used neat. The results of experiment 3 are listed in Table 2. Laminates with the pigment B2 show a significantly higher opacity compared to pigment A1 as standard, but are less good compared to pigment B1. Pigment B2 also shows insufficient graying stability. There are no disadvantages with respect to wet tear strength.
In diesem Versuch wird eine Pigmentmischung bestehend aus 70 Gew.-% Pigment A1 und 30 Gew.-% Pigment B2 eingesetzt. Die Ergebnisse von Versuch 4 sind in Tabelle 2 aufgeführt. Dieses Laminat mit einem 70 : 30 Pigmentgemisch zeigt eine verbesserte Opazität im Vergleich zu Versuch 1. Die Vergrauungsstabilität ist noch akzeptabel.In this experiment, a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B2 is used. The results of experiment 4 are listed in Table 2. This laminate with a 70:30 blend shows improved opacity compared to Run 1. Graying stability is still acceptable.
In diesem Versuch wird eine Pigmentmischung bestehend aus 70 Gew.-% A1 und 30 Gew.-% B3 eingesetzt. Letzteres basiert auf einem hellen, leicht stabilisierten Grundkörper mit einer "klassischen Laminatpigment-" und einer zusätzlichen "Dispersionsfarbenpigment-Nachbehandlung". Die Ergebnisse von Versuch 5 sind in Tabelle 2 aufgeführt. Das oben genannte Pigmentgemisch führt zu Laminaten mit deutlich verbesserter Opazität im Vergleich zu Versuch 1, die Vergrauungsstabilität liegt auf einem akzeptablen Niveau.In this experiment, a pigment mixture consisting of 70 wt .-% A1 and 30 wt .-% B3 is used. The latter is based on a light, slightly stabilized base body with a "classic laminate pigment" and an additional "dispersion paint pigment aftertreatment". The results of experiment 5 are in Table 2 listed. The abovementioned pigment mixture leads to laminates with markedly improved opacity compared to Experiment 1, the graying stability is at an acceptable level.
In diesem Versuch wird eine Pigmentmischung bestehend aus 70 Gew.-% Pigment A1 und 30 Gew.-% Pigment B4 eingesetzt. Pigment B4 ist ähnlich oberflächenbehandelt wie Pigment B1, allerdings mit einem hochstabilisierten Grundkörper hergestellt. Die Ergebnisse sind in Tabelle 2 aufgeführt. Es ist erkennbar, dass der Übergang zu einem hochstabilisierten Grundkörper die Vergrauungstabilität deutlich verbessert. Die Laminate zeigen eine deutlich verbesserte Opazität im Vergleich zu Versuch 1. Die Nassreißfestigkeit der Papiere ist niedriger als bei reinem A1, aber auf einem akzeptablen Niveau.In this experiment, a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B4 is used. Pigment B4 is similarly surface-treated as Pigment B1, but made with a highly stabilized base. The results are shown in Table 2. It can be seen that the transition to a highly stabilized base body significantly improves graying stability. The laminates show a significantly improved opacity compared to Experiment 1. The wet tensile strength of the papers is lower than with pure A1, but at an acceptable level.
In diesem Versuch wird eine Pigmentmischung bestehend aus 70 Gew.-% Pigment A1 und 30 Gew.-% Pigment B5 eingesetzt. Letzeres ist ein Pigment ähnlich oberflächenbehandelt wie Pigment B4, allerdings mit ca. 25 % weniger SiO2-Oberflächenbehandlung hergestellt. Die Ergebnisse von Versuch 7 sind in Tabelle 2 aufgeführt. Diese Mischung zeigt wegen der geringeren SiO2 Oberflächenbehandlung von B5 im Vergleich zu B4 gegenüber Versuch 6 eine schlechtere Opazität bei vergleichbarer Vergrauungsstabilität.In this experiment, a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B5 is used. The latter is a pigment similar to surface treated pigment B4 but made with about 25% less SiO 2 surface treatment. The results of experiment 7 are listed in Table 2. This mixture shows due to the lower SiO 2 surface treatment of B5 compared to B4 compared to Experiment 6 inferior opacity with comparable graying stability.
In diesem Versuch wird eine Pigmentmischung bestehend aus 70 Gew.-% Pigment A1 und 30 Gew.-% Pigment B6 eingesetzt. Pigment B6 ist ähnlich oberflächenbehandelt wie Pigment B2, allerdings mit der doppelten Menge SiO2. Es wird der hochstabilisierte Grundkörper wie bei B4 eingesetzt. Die Ergebnisse von Versuch 8 sind in Tabelle 2 aufgeführt. Die Opazität des Laminatmusters mit diesem Pigmentgemisch liegt deutlich über der mit reinem A1. Die Nassreißfestigkeit ist ausreichend, die Vergrauungsstabilität ist gut.In this experiment, a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B6 is used. Pigment B6 is similarly surface-treated as pigment B2, but with twice the amount of SiO 2 . The highly stabilized base body is used as in B4. The results of experiment 8 are listed in Table 2. The opacity of the laminate pattern with this pigment mixture is significantly higher than that with pure A1. The wet tear strength is sufficient, the graying stability is good.
In diesem Versuch wird eine Pigmentmischung bestehend aus 70 Gew.-% Pigment A1 und 30 Gew.-% Pigment B7 eingesetzt. Letzteres Pigment ist ähnlich oberflächenbehandelt wie Pigment B6. Die Ergebnisse von Versuch 9 sind in Tabelle 2 aufgeführt. Dieses Pigmentgemisch führt auf Grund einer gegenüber Versuch 8 erhöhten SiO2-Menge zu einem Laminat mit höchsten Opazitätswerten, deutlich höher im Vergleich zu reinem Pigment A1. Die Vergrauungsstabilität liegt auf einem guten Niveau. Die Nassreißfestigkeit der Papiere mit o. g. Pigmentmischung ist tolerierbar an der oberen Grenze.In this experiment, a pigment mixture consisting of 70% by weight of pigment A1 and 30% by weight of pigment B7 is used. The latter pigment is similarly surface-treated as pigment B6. The results of experiment 9 are listed in Table 2. Due to an amount of SiO 2 increased compared to Experiment 8, this pigment mixture leads to a laminate with highest opacity values, significantly higher in comparison with pure pigment A1. The graying stability is at a good level. The wet tensile strength of the papers with the above-mentioned pigment mixture is tolerable at the upper limit.
Es werden Titandioxid-Pigmentzusammensetzungen bevorzugt, bei denen der Anteil des Pigmenttyps B 10 bis 90 Gew.-%, besonders bevorzugt 30 bis 50 Gew.-%, an der Pigmentmischung beträgt.
Claims (7)
- Titanium dioxide pigment composition containing,
as pigment type (A), a post-treated pigment with high greying resistance, where the greying value CIELAB ΔL* (DIN 6174) is less than 1.5 after 96 hours of exposure in the Xenotest, and,
as pigment type (B), a pigment inorganically post-treated with Si and Al compounds precipitated in flaky form,
where the Al content of pigment type (B) is at least 2% by weight (calculated as Al2O3), the Si content is at least 3% by weight (calculated as SiO2) and the sum of SiO2 and Al2O3 is at least 7% by weight (referred to the base material in each case). - Titanium dioxide pigment composition according to Claim 1, characterised in that pigment type (B)
either displays a rutile base material from the chloride process that is doped with Al to a level of 0.3 to 3.0% by weight (calculated as Al2O3) and manufactured with an oxygen excess of 2 to 15% during gas-phase oxidation of the TiCl4 into TiO2,
or displays a rutile base material from the sulphate process that is doped with Al, Sb, Nb or Zn. - Titanium dioxide pigment composition according to Claim 1 or 2, characterised in that
pigment type (B) displays a base material that is manufactured by the sulphate process and doped with up to 1% by weight Al (calculated as Al2O3). - Titanium dioxide pigment composition according to one or more of Claims 1 to 3, characterised in that
pigment type (B) is initially coated with aluminium phosphate, applied directly to the base material. - Titanium dioxide pigment composition according to one or more of Claims 1 to 4, characterised in that
pigment type (B) is additionally coated with up to 0.2% by weight Ce (calculated as CeO2) and/or with up to 2.5% by weight Zn (calculated as ZnO). - Titanium dioxide pigment composition according to one or more of Claims 1 to 5, characterised in that
pigment type (B) displays a nitrate content of up to 1% by weight (referred to the base material) and/or is subjected to tempering up to 500 °C. - Titanium dioxide pigment composition according to one or more of Claims 1 to 6, characterised in that
the proportion of pigment type (B) relative to the pigment mixture is 10 to 90% by weight, preferably 30 to 50% by weight.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10115544 | 2001-03-28 | ||
DE10115544A DE10115544A1 (en) | 2001-03-28 | 2001-03-28 | Titanium dioxide pigment composition |
PCT/DE2002/000863 WO2002077107A2 (en) | 2001-03-28 | 2002-03-12 | Titanium dioxide pigment composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1373412A2 EP1373412A2 (en) | 2004-01-02 |
EP1373412B1 true EP1373412B1 (en) | 2010-04-28 |
Family
ID=7679538
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Application Number | Title | Priority Date | Filing Date |
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EP02727212A Expired - Lifetime EP1373412B1 (en) | 2001-03-28 | 2002-03-12 | Titanium dioxide pigment composition |
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US (1) | US6962622B2 (en) |
EP (1) | EP1373412B1 (en) |
JP (1) | JP4309659B2 (en) |
BR (1) | BR0208391B1 (en) |
CA (1) | CA2441852C (en) |
CZ (1) | CZ301559B6 (en) |
DE (2) | DE10115544A1 (en) |
ES (1) | ES2342260T3 (en) |
NO (1) | NO20034313L (en) |
PL (1) | PL204504B1 (en) |
WO (1) | WO2002077107A2 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2511095A1 (en) | 2002-12-30 | 2004-07-22 | E. I. Du Pont De Nemours And Company | Process of making a water dispersible titanium dioxide pigment useful in paper laminates |
ES2299790T3 (en) * | 2004-12-23 | 2008-06-01 | Evonik Degussa Gmbh | TITANIUM DIOXIDES PRODUCED BY VIA PIROGENA AND SUPERFICIALLY MODIFIED. |
US7265176B2 (en) * | 2005-01-31 | 2007-09-04 | E. I. Du Pont De Nemours And Company | Composition comprising nanoparticle TiO2 and ethylene copolymer |
US7824486B2 (en) * | 2005-09-27 | 2010-11-02 | E. I. Du Pont De Nemours And Company | Paper laminates |
US20070068423A1 (en) * | 2005-09-27 | 2007-03-29 | Thiele Erik S | Titanium dioxide pigment useful in paper laminates |
US20070137526A1 (en) * | 2005-12-19 | 2007-06-21 | Tronox Llc | Method for making high tint strength pigment compositions |
DE102006012564B4 (en) | 2006-03-16 | 2008-11-06 | Kronos International, Inc. | Titanium dioxide pigment coated with hollow microspheres and method of manufacture |
US7288146B1 (en) | 2006-03-16 | 2007-10-30 | Kronos International, Inc. | Titanium dioxide pigment coated with hollow bodies and method for its manufacture |
US8840719B2 (en) | 2011-03-09 | 2014-09-23 | Tronox Llc | Titanium dioxide pigments and manufacturing method |
US9481797B2 (en) | 2011-08-09 | 2016-11-01 | Cristal Usa Inc. | Pigment for paper and paper laminate |
DE102013009390A1 (en) | 2012-06-29 | 2014-01-02 | Kronos International, Inc. | Process for the surface treatment of inorganic pigment particles |
CA2891157C (en) | 2012-11-13 | 2020-12-15 | E. I. Du Pont De Nemours And Company | Decor paper comprising self-dispersing pigments |
WO2014078043A1 (en) | 2012-11-13 | 2014-05-22 | E. I. Du Pont De Nemours And Company | Laminates prepared from décor paper comprising self-dispersing pigments |
EP2920249B1 (en) | 2012-11-13 | 2020-04-01 | The Chemours Company FC, LLC | Self-dispersing pigments |
JP6231120B2 (en) | 2012-11-13 | 2017-11-15 | ザ ケマーズ カンパニー ティーティー リミテッド ライアビリティ カンパニー | Method for preparing self-dispersing pigments |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3510335A (en) * | 1965-10-22 | 1970-05-05 | Du Pont | Titanium pigment production |
US4075031A (en) * | 1976-09-30 | 1978-02-21 | E. I. Du Pont De Nemours And Company | TiO2 Pigment coated with dense silica and porous alumina/silica |
JP2585128B2 (en) * | 1989-06-02 | 1997-02-26 | テイカ株式会社 | Colored fine particle inorganic pigment |
GB8918056D0 (en) * | 1989-08-08 | 1989-09-20 | Tioxide Group Plc | Corrosion inhibiting pigment |
US5346546A (en) * | 1991-07-22 | 1994-09-13 | Industrial Progress, Inc. | Aggregate-TiO2 pigment products |
US5342485A (en) * | 1992-08-05 | 1994-08-30 | Reynolds Metals Company | Process for preparing ultra-white alumina trihydrate |
TW370552B (en) * | 1994-11-09 | 1999-09-21 | Du Pont | Process for making rutile titanium dioxide pigment comprising coated titanium dioxide particles |
FR2758826B1 (en) * | 1997-01-27 | 1999-04-16 | Rhodia Chimie Sa | NOVEL TITANIUM DIOXIDE PIGMENT, PROCESS FOR PREPARING IT, AND USE THEREOF IN PAINT COMPOSITIONS |
-
2001
- 2001-03-28 DE DE10115544A patent/DE10115544A1/en not_active Withdrawn
-
2002
- 2002-03-12 BR BRPI0208391-4A patent/BR0208391B1/en not_active IP Right Cessation
- 2002-03-12 PL PL362799A patent/PL204504B1/en unknown
- 2002-03-12 CA CA2441852A patent/CA2441852C/en not_active Expired - Fee Related
- 2002-03-12 US US10/468,048 patent/US6962622B2/en not_active Expired - Lifetime
- 2002-03-12 CZ CZ20032866A patent/CZ301559B6/en not_active IP Right Cessation
- 2002-03-12 WO PCT/DE2002/000863 patent/WO2002077107A2/en active Application Filing
- 2002-03-12 EP EP02727212A patent/EP1373412B1/en not_active Expired - Lifetime
- 2002-03-12 JP JP2002576557A patent/JP4309659B2/en not_active Expired - Fee Related
- 2002-03-12 DE DE50214399T patent/DE50214399D1/en not_active Expired - Lifetime
- 2002-03-12 ES ES02727212T patent/ES2342260T3/en not_active Expired - Lifetime
-
2003
- 2003-09-26 NO NO20034313A patent/NO20034313L/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
CZ20032866A3 (en) | 2004-01-14 |
DE50214399D1 (en) | 2010-06-10 |
CA2441852C (en) | 2012-07-10 |
WO2002077107A3 (en) | 2003-02-06 |
US20040094068A1 (en) | 2004-05-20 |
NO20034313D0 (en) | 2003-09-26 |
PL362799A1 (en) | 2004-11-02 |
DE10115544A1 (en) | 2002-10-10 |
WO2002077107A2 (en) | 2002-10-03 |
BR0208391B1 (en) | 2012-09-04 |
NO20034313L (en) | 2003-09-26 |
PL204504B1 (en) | 2010-01-29 |
ES2342260T3 (en) | 2010-07-05 |
JP2004525850A (en) | 2004-08-26 |
JP4309659B2 (en) | 2009-08-05 |
EP1373412A2 (en) | 2004-01-02 |
BR0208391A (en) | 2004-06-15 |
US6962622B2 (en) | 2005-11-08 |
CZ301559B6 (en) | 2010-04-14 |
CA2441852A1 (en) | 2002-10-03 |
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